Composition for the permanent shaping of human hair

ABSTRACT

The present invention concerns a composition for the permanent shaping of human hair used both for the permanent waving of human hair with an excellent waving effect as well as for the straightening of curled hair comprising at least one ubichinone of the formula 
                         
where n is a number between 1 and 10 at a concentration of 0.0001 to 1% by weight calculated to total composition.

The present invention concerns a composition for the permanent shapingof human hair used both for the permanent waving of human hair with anexcellent waving effect as well as for the straightening of curled hair.

It is generally known that permanent waving is carried out in two steps,the reductive splitting of the cysteine disulfide bonds in the hair by areducing agent, and the subsequent neutralization by application of anoxidizing agent, whereby the cysteine disulfide bonds are restored.

The reducing agent still most frequently used today is thioglycolicacid, also in form of the salts thereof, in particular its ammoniumsalt, although numerous other thio compounds have been proposed for thispurpose, which, however, mostly did not succeed.

The compositions containing thioglycollates are customarily applied at apH-value between 7 and 10, in particular 8.5 and 9.5.

Such compositions vary in their waving and/or straightening performanceand, therefore, there is still need for further improvement.

The present invention starts from the task of providing a compositionfor the permanent shaping of human hair with excellent waving andstraightening performance. Hair waved or straightened with compositiondisclosed herein looks and feels natural upon touching by hand.

Accordingly, the first object of the present invention is a compositionfor permanent shaping and/or straightening hair based on at least onereducing agent, which further comprises at least one ubichinone of theformula

where n is a number between 1 and 10. Preferred ubichinones are the oneswhere n is a number between 6 and 10 and especially preferred isUbichinone 50 where n is 10, also known as Coenzyme Q10.

Ubichinones have been used in cosmetic compositions. Such compositionshave been disclosed for example in EP 751 762 B1 for hair conditioningcompositions in combination with retinols, in DE 199 26 167 A1 and DE199 26 168 A1 for hair styling compositions, DE 199 26 170 A1 forcleansing preparations and in DE 199 26 156 A1 for hair conditioningcompositions. Furthermore, in EP 1232 741 A1 the use of ubichinones inhair colouring compositions is disclosed.

In none of the patent documents mentioned above, a permanent shapingcomposition for hair comprising ubichinone is neither disclosed normentioned.

Concentration of at least one ubichinone of the above formula inpermanent shaping compositions of the present invention is from 0.0001to 1%, preferably from 0.0002 to 0.75%, more preferably from 0.0002 to0.5% and most preferably from 0.0005 to 0.5% by weight, calculated tototal composition.

The permanent waving compositions according to the invention comprisesat least one reducing compound. Preferred are thioglycolic acid andthiolactic acid as well as the salts thereof, in particular the ammoniumand ethanolamine salts. Further useful thio compounds are in particularcysteine or the hydrochloride thereof, homocysteine, cysteamine,N-acetyl cysteine, thioglycerol, ethanediol monothioglycollate,1.2-propyleneglycol monothioglycollate (see also WO-A 93/1791),1-3-propanediol monothioglycollate or the isomer mixture resultingtherefrom, 1.3-butanediol and 1.4-butanediol monothioglycollate and theisomer mixtures therefrom, polyethylene glycol, such as di-, tri- andtetraethyleneglycol monothioglycollates, glycerol monothiolactate andfurther thio acids and the esters thereof, as well as mixtures thereof.

The use of inorganic reducing sulfur compounds such as sodium hydrogensulfite is basically also possible.

The total reduction agent content in the compositions according to theinvention customarily amounts from 2.5% to about 15% by weight,calculated to total composition as free thioglycolic acid as referencesubstance.

The waving compositions containing reducing agents can, if necessary,comprise alkalizing agents. Their quantity is dependent on the reducingagent and the desired pH-value of the composition. Reducing agentcompositions preferably contain about 0.1% to about 5%, in particularabout 0.5% to about 2.5% by weight thereof, calculated to the totalcomposition. Alkalizing agents preferred within the scope of theinvention are ammonium carbamate, ammonia and/or ammonium(bi)carbonate,and triethanolamine. It is desirable to adjust the pH-value betweenabout 6.5 and 10.5, preferably about 7 to 9.5.

The shaping compositions according to the invention are suited for useboth for the permanent waving, i.e. curling of human hair and for thestraightening, i.e. smoothing thereof.

The viscosity best suited for the permanent waving compositionsaccording to the invention proved to be in the range of about 500 to10,000 mPa·s, preferably about 1,000 to about 5,000 mPa·s, measured at20° C. in a Brookfield viscosimeter (no. 5 spindle), whereas theviscosity suited for the straightening compositions is preferably higherin a range up to about 50,000 mPa·s, preferably up to 30,000 mPa·smeasured at 20° C. in a Brookfield viscosimeter (no. 5 spindle).

The viscosity is adjusted by addition of the appropriate amounts ofthickening agents known per se, such as cellulose derivatives.Thickening may as well be realised by formulating a composition in formof an emulsion with the use of C₁₀-C₂₂-fatty alcohols, in admixture withlong mono alkyl chain quaternary ammonium surfactants.

The permanent waving compositions according to the present inventionpreferably comprise surfactants selected from anionic, nonionic,cationic and amphoteric ones. Their proportion ranges from about 0.05%to about 10%, in particular from about 0.1% to about 5% by weight,calculated to total composition.

Suitable anionic surfactants are especially the known alkyl ethersulfates and carboxylic acids, in particular in form of their alkalisalts, as well as protein fatty acid condensates.

Suitable nonionic surfactants, which are preferred within the scope ofthe invention, are in particular C₈-C₁₈-fatty alcohol polyglycol ethers,fatty acid polyglycol esters, fatty acid alkanolamides, amineoxides, andespecially C₈-C₁₈-alkyl polyglucosides.

Also possible is the incorporation of amphoteric surfactants, such asthe known alkyl betaines, alkyl amido betaines, and alkyl amphoacetates.

Further according to a further preferred embodiment, permanent shapingcompositions comprise at least one cationic surfactant according togeneral formula

where R₁s a saturated or unsaturated, branched or non-branched alkylchain with 8-22 C atoms orR₅CONH(CH₂)_(n)where R₅ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4 orR₆COO(CH₂)_(n)where R₆ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4, andR₂ is a hydrogen, saturated or unsaturated, branched or non-branchedalkyl chain with 1-22 C atoms orR₅CONH(CH₂)_(n)where R₅ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4 orR₆COO(CH₂)_(n)where R₆ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4,and R₃ and R₄ are independent from each other H or lower alkyl chainwith 1 to 4 carbon atoms, and X is chloride, bromide or methosulfate.

Concentration of at least one cationic surfactant is in the range from0.05% to 5%, preferably 0.1% to 2.5% by weight, calculated to totalcomposition.

Suitable long-chain quaternary ammonium compounds which can be usedalone or in admixture are in particular cetyl trimethyl ammoniumchloride, dimethyl dicetyl ammonium chloride, trimethyl cetyl ammoniumbromide chloride, stearyl trimethyl ammonium chloride, dimethyl stearylbenzyl ammonium chloride, benzyl tetradecyl dimethyl ammonium chloride,dimethyl dihydrogenated tallow ammonium chloride, lauryl pyridiniumchloride, lauryl dimethyl benzyl ammonium chloride, lauryl trimethylammonium chloride, tris-(oligooxyethyl) alkyl ammonium phosphate, cetylpyridinium chloride, etc.

In a further preferred embodiment of the present invention, thecompositions comprise at least one cationic polymer. Basically suitableare all cationic polymers listed under the generic name “Polyquaternium”and “Quaternium” in the CTFA International Cosmetic IngredientDictionary. Examples are Polyquaternium 6, Polyquaternium 7,Polyquaternium 10, Polyquaternium 11, Polyquaternium 16, Polyquaternium22 and Polyquaternium 28, Polyquaternium 39, Quaternium-8,Quaternium-14, Quaternium-15, Quaternium-18, Quaternium-22,Quaternium-24, Quaternium-26, Quaternium-27, Quaternium-30,Quaternium-33, Quaternium-53, Quaternium-60, Quaternium-61,Quaternium-72, Quaternium-78, Quaternium-80, Quaternium-81,Quaternium-81, Quaternium-82, Quaternium-83 and Quaternium-84.

The cationic polymers also include the quaternized products of graftpolymers from organopolysiloxanes and polyethyl oxazolines described inEP-A 524 612 and EP-A 640 643.

Concentration of one or more cationic polymers is in the range from0.05% to 5%, preferably 0.1% to 2.5% by weight, calculated to totalcomposition.

Permanent shaping compositions of present invention can compriseadditionally at least one organic solvent. Suitable organic solvents are2-methyl-1,3-propanediol, mono and dialcohols or the ethers thereof, inparticular mono-C₁-C₃-alkyl ether, ethanol, n-propanol, isopropylalcohol, 1-methoxypropanol, 1-ethoxypropanol and ethoxydiglycol, diolsand their esters 1,3- and 1,4-butanediol, diethyleneglycol and themonomethyl and monoethyl ether thereof, dipropylene glycol and themonomethyl and monoethyl ether thereof, glycerol, hexanetriol, ethylcarbitol, benzyl alcohol, benzyloxy ethanol, propylene carbonate,N-alkyl pyrrolidone, and urea or their mixture preferably in an amountfrom about 0.1% to 10% by weight, calculated to the total composition.

Permanent shaping composition of the present invention can comprisefurther ceramide type of compound with the general formula

-   -   where R₇ and R₈ are independent from each other alkyl- or.        alkenyl group with 10 to 22 carbon atoms, R₉ is alkyl or        hydroxyl alkyl with 1 to 4 carbon atoms group and n is a number        between 1 to 6, preferably 2 or 3. Preferred compound according        to the above chemical structure is        cetyl-PG-hydroxyethylpalmitamide.

Further optional ingredient are sterols, especially the phytosterols aspreferred hair restructuring agents. Especially preferred ones are ofplant origin for example ergosterol, sitosterol, stigmasterol,fucosterol, brassicasterol, fungisterol, campesterol, zymosterol,ascosterol, cerevisterol, episterol, faecosterol, spinasterol. Amongthose phytosterols, the ones found in “Avocadin” which is theunsaponified fraction of the avocado oil is more preferred.

Optionally fatty acids of C10 to C22 may be incorporated into thecompositions of the present invention at a concentration of preferably0.01 to 2.5% by weight calculated to total composition.

Another preferred compound in the permanent shaping composition of thepresent invention is silicone compounds and especially aminatedsilicones such as amodimethicone available from for example Dow Corningunder the brand names Dow Corning 949 Emulsion and Dow Corning 2-8194.Concentration of silicones, especially amodimethicone, is in the rangeof 0.05 to 2.5%, preferably 0.1 to 1% by weight calculated to totalcomposition.

Additionally, one or more natural oil component may be incorporated intothe compositions of the present invention. Suitable are such as oliveoil, almond oil, avocado oil, wheatgerm oil, ricinus oil or theirmixture. Concentration of these natural oil ingredients should be 0.01to 2.5%, preferably 0.01. to 1%, more preferably 0.05 to 0.5% by weight,calculated to total composition.

The compositions used according to the invention can naturally compriseall the substances customarily found in permanent shaping compositions,a list of which will not be given here, and are preferably present assolutions, gels with a higher or lower viscosity, emulsions or creams.They can be single-phase products or compositions packed into separatepackaging which are united upon application, as they are disclosed, forexample, in DE-C 43 04 828.

In order to avoid repetition, reference is here made to the state of theart as it is described, for example, in “Ullmann's Encyclopedia ofIndustrial Chemistry”, Vol. A12 (1986), pages 588 to 591, and inparticular to the monography of K. Schrader, “Grundlagen und Rezepturender Kosmetika”, 2^(nd). Ed. (1989, Hüthig Buchverlag) pages 823 to 840,as well as the article by D. Hollenberg et. al. in“Seifen-Öle-Fette-Wachse”, 117 (1991), pages 81 to 87.

Composition of the present invention is used in a process for permanentwaving wherein hair is washed or shampooed first and wound on thecurlers, subsequently a reducing agent comprising composition with atleast one ubichinone is applied onto hair and after 1 to 45 min,preferably 1 to 30 min of processing time, depending on the hairstrength, rinsed off from hair with tap water and an oxidizingcomposition comprising at least one oxidizing agent, preferably hydrogenperoxide or sodium bromate at a concentration of 0.5 to 10% by weightcalculated to total of oxidizing composition, is applied onto hair andleft on the hair 1 to 20 min and rinsed off and curlers removed fromhair. In cases where additional conditioning composition is requiredthis may as well be applied.

In another process as described above the curlers are removed afterrinsing off the reducing agent and before applying the oxidizing agent.

Further in another process, after rinsing off the reducing agent fromhair, an intermediate treatment composition is applied onto hair andwithout rinsing off but after removing the excess amount of intermediatetreatment with a towel, oxidizing composition is applied and at the endof the processing they are rinsed off from hair and criers are removedfrom hair. It has further been found out that the use of ubichinone inthe intermediate treatment composition in the same concentration rangeas disclosed above for the reducing composition improves the permanentshaping of hair as well in terms of curl appearance and natural look andfeel of hair. Therefore in another preferred form of the presentinvention, permanent shaping of hair is carried our with a processwherein hair is washed or shampooed first and subsequently a reducingagent comprising composition is applied onto hair and after 1 to 45 min,preferably 1 to 30 min of processing time, depending on the hairstrength, rinsed off from hair with tap water and an intermediatetreatment composition comprising at least one ubichinone of the formulaabove and magnesium sulfate at a concentration of 2 to 15% by weight isapplied and without rinsing off an oxidizing composition comprising atleast one oxidizing agent, preferably hydrogen peroxide or sodiumbromate at a concentration of 0.5 to 10% by weight calculated to totalof oxidizing composition, is applied onto hair and left on the hair 1 to20 min and rinsed off. In cases where additional conditioningcomposition is required this may as well be applied.

The intermediate treatment composition has a pH value between 2.5 to 6,preferably 3 to 5.5 and most preferably 3 to 5.

A straightening process may also be carried out in a different processwherein hair is washed and/or shampooed and dried and reducingcomposition comprising at least one ubichinone is applied onto dry hairand processed for 5 to 60 min, preferably 5 to 45 min and rinsed offwith water and dried and the dry hair physically straighten with hotiron at a temperature of 130 to 210° C. and subsequently an oxidizingcomposition comprising at least one oxidizing agent, preferably hydrogenperoxide or sodium bromate at a concentration of 0.5 to 10% by weightcalculated to total of oxidizing composition, is applied onto hair andleft on the hair 1 to 20 min and rinsed off.

The following examples are to illustrate the invention, but not to limitit.

EXAMPLE 1 Alkaline Permanent Wave for Normal Hair

Ammonium thioglycolate (60%) 21.3 (% by wt. Ammonium hydrogen carbonate5.0 1,3-butylene gylcol 3.0 Amodimethicone 0.2 PEG-40-Hydrogenatedcastor oil 0.7 Polyquaternium-7 0.5 Perfume 0.4 Coenzyme Q10 0.04Ammonia, 25% ad pH 8.3 Water ad 100.0

With this composition the hair was permanently waved for about 15minutes, rinsed and neutralized for about 8 minutes with a customary2.5% H₂O₂ composition. Homogeneous wave appearance was obtained.Exclusion of Coenzyme Q10 resulted in less homogeneous perm appearance.

EXAMPLE 2 Alkaline Permanent Wave for Damaged Hair

Ammonium thioglycollate (60%) 15.0 (% by wt.) Ammonium hydrogencarbonate 2.5 Ceteth-20 0.7 Tallow trimonium chloride 0.1 1,3-butylenegylcol 0.5 Polyquaternium-6 1.5 Amodimethicone 0.2 Coenzyme Q10 0.1Oleic acid 0.05 Perfume 0.4 Ammonia, 25% ad pH 8.0 Water ad 100.0

The permanent wave achieved with this composition was similar to the oneobtained with the composition according to Example 1.

Exclusion of the ubichinone led to waves with substantially weakercontours.

EXAMPLE 3 Alkaline Permanent Wave for Damaged Hair

Ammonium thioglycollate (60%) 0.9 (% by wt.) Cystein hydrochloride 5.7Ammonium hydrogen carbonate 1.5 Acetylcystein 0.7 Cetrimonium chloride0.1 1,3-butylene gylcol 0.5 Polyquaternium-39 1.5 Amodimethicone 0.2Coenzyme Q10 0.1 Oleic acid 0.05 Perfume 0.4 Ammonia, 25% ad pH 9.8Water ad 100.0

The permanent wave achieved with this composition was similar to the oneobtained with the composition according to Example 1.

Exclusion of the ubichinone led to substantially weaker waves.

EXAMPLE 4 Neutral Permanent Wave for Normal Hair

A permanent waving product consisting of two Compositions A and B,filled into a two-chamber packaging the chambers of which were keptseparate until application, was prepared by destruction of theseparating wall and applied onto human hair rolled onto curlers. Thehair was rinsed after about fifteen minutes processing and neutralizedfor about five minutes with a 2.5% H₂O₂ neutralizer composition, rinsedagain, shampooed and dried.

An expressive, even, intensive permanent wave was obtained.

An identical treatment which had no Ubichinone showed a visibly inferiorwave.

Composition A:

Ammonium hydrogen carbonate 4.5 (g) Polyquaternium-6 1.0PEG-65-Hydrogenated castor oil 0.8 Isopropyl alcohol 1.5 Ethoxydiglycol2.0 Cocoamidopropyl betaine 1.0 Perfume 0.3 Coenzyme Q10 0.05Turbidifying agent 0.5 Ammonia, 25% ad pH 8.4 Water ad 72.0Composition B:

Ammonium thioglycollate, 70% 18.0 (g) Thiolactic acid 2.02-Methyl-1.3-propanediol 0.5 Ammonia, 25% ad pH 5.5 Water ad 28.0

After admixture of both Compositions a ready-to-use product with apH-value of 7.4 was obtained.

EXAMPLE 5 Neutral Permanent Wave for Dyed Hair

A permanent waving product filled into a two-chamber package wasprepared in analogy to Example 3:

Composition A:

Ammonium hydrogen carbonate 3.5 (g) Polyquaternium-11 0.5 Ethanol 0.51-Methoxypropanol 1.0 Cocoamidopropyl betaine 1.0 PEG-25-glycerylcocoate 0.8 Coenzyme Q10 0.1 Oleic acid 0.05 Perfume 0.3 Turbidifyingagent 0.5 Ammonia, 25% ad pH 8.3 Water ad 72.0Composition B:

Ammonium thioglycollate, 70% 13.0 (g) Thiolactic acid 0.52-Methyl-1.3-propanediol 1.5 Ammonia, 25% ad pH 5.5 Water ad 28.0

A product with a pH-value of 7.4 was obtained by admixture of theCompositions immediately prior to application. After application ontodyed hair as described in Example 3, this mixture resulted in anexpressive permanent wave, which had not effect whatever on the colorgloss and color intensity.

EXAMPLE 6 Alkaline Permanent Waving Gel

Ammonium thioglycollate, 70% 15.0 (g) Ammonium hydrogen carbonate 4.5PEG-40-Hydrogenated castor oil 0.7 C₁₂-C₁₈-Fatty alcohol mixture 3.5Cetrimonium chloride 2.0 Amodimethicone 0.05 2-Methyl-1.3-propanediol0.5 Polyquaternium-28 0.1 Coenzyme Q10 0.1 Perfume 0.3 Ammonia, 25% adpH 8.0 Water ad 100.0Intermediate Treatment Composition

Asparagic acid 0.25% by weight Glutamic acid 0.50 Alanin DL 0.25Magnesium sulfate 10.00 Coenzyme Q10 0.05 Water q.s. to 100

The above composition had a pH of 4.10.

EXAMPLE 7 Straightening Composition

Thioglycolic acid 8.0 (% by wt.) C₁₆-C₂₂-Fatty alcohol mixture 3.5Oleth-50 2.5 Laureth-23 1.5 Polyquaternium-2 0.8 Coenzyme Q10 0.1 Oleicacid 0.1 Ethanol 5.0 Perfume 0.6 Monoethanolamine ad pH 9.3 Water ad100.0

This composition constitutes an effecting smoothing composition forkinky hair.

1. Composition for the permanent shaping of human hair, comprising atleast one reducing agent selected from the group consisting ofthioglycolic acid, thiolactic acid and salts of thiolactic acid at aconcentration of between 5 to 15% by weight based on the total weight ofthe composition, and at least one ubichinone of the formula

where n is a number between 1 and
 10. 2. Composition according to claim1, wherein the composition has a Brookfield viscosity of 500 to 10,000mPa·s at 20° C.
 3. Composition according to claim 1 comprising at leastone surfactant selected from anionic, nonionic, cationic and amphotericones at a concentration of 0.05 to 10% by weight, calculated to totalcomposition.
 4. Composition according to claim 1 comprising at least onecationic polymer at a concentration of 0.05 to 5% by weight, calculatedto total composition.
 5. Composition according to claim 1 comprising atleast one organic solvent at a concentration of 0.1 to 10% by weight,calculated to total composition.
 6. Composition according to claim 1comprising at least one silicone compound at a concentration of 0.05 to2.5% by weight, calculated to total composition.
 7. Compositionaccording to claim 1 comprising at least one fatty acid with 10 to 22 Catoms at a concentration of 0.01 to 2.5% by weight, calculated to totalcomposition.
 8. Composition according to claim 6 wherein the siliconecompound is an aminated silicone.
 9. Composition according to claim 1wherein the reducing agent is present at a concentration of between 5 to13% by weight based on the total weight of the composition. 10.Composition according to claim 1 wherein the reducing agent is presentat a concentration of between 5 to 8% by weight based on the totalweight of the composition.